Mh. Hung et Wb. Farnham, THERMAL-DECOMPOSITION OF FLUORINATED DIOXOLANE CARBOXYLATES, Journal of the Chinese Chemical Society, 40(6), 1993, pp. 563-569
Synthesis of fluorodioxole olefin monomers by thermal decomposition of
fluorinated dioxolane carboxylic acid and the corresponding acyl chlo
ride was explored. Complex product formation is observed, including ac
yl fluoride from Cl-F exchange, the hydro-dioxolane from proton abstra
ction, the cyclic ether ketone from dioxolane ring opening, and the ep
oxy acid fluoride from thermal rearrangement. The product distribution
is strongly dependent upon reaction conditions. The main influential
factors include the reaction temperature, the base used for the reacti
on, the presence or absence of solvent, and the counter ion associated
with the intermediate salt. A mechanism is proposed to rationalize bo
th the results and the product distribution. Methods to make authentic
samples for product analysis are reported.